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The use of electromagnetic fields to control a collection of magnetic nanoparticles, known as a microswarm, has many promising applications. Current research often makes use of accurate but time-consuming simulations lacking real-time human input. On the contrary, human interaction is possible with a real-time simulator, allowing the collection of valuable user interaction data. This paper presents the development and validation of a real-time two-dimensional microswarm simulator to accommodate the human interaction aspect. A haptic device is used to steer the microswarm through a multi-bifurcation vascular network towards a selected outlet. The percentage of particles reaching the selected outlet is used as the success metric. The simulator is verified against collected real-world experimental data and shows an 8% deviation. Parametric studies demonstrate the most influential parameters. We found that reducing the magnetic gradient from 1000 mT/m to 100 mT/m resulted in a decrease in recorded performance from 100% to 30.8%. Variation in fluid flow also had a considerable effect on the recorded performance, presenting a drop from 100% to 35.3% when fluid flow velocities increased from 0.005 m/s to 0.06 m/s. Changing the starting arrangement of particles resulted in a drop to 59% over the same range of fluid flow velocities.

Cardiovascular disease (CVD) represents a major public health issue, claiming numerous lives. This study aimed to demonstrate the advantages of employing artificial intelligence (AI) models to improve the prediction of CVD risk using a large cohort of relatively healthy adults aged 70 years or more. In this study, deep learning (DL) models provide enhanced predictions (DeepSurv: C-index = 0.662, Integrated Brier Score (IBS) = 0.046; Neural Multi-Task Logistic Regression (NMTLR): C-index = 0.660, IBS = 0.047), as compared to the conventional (Cox: C-index = 0.634, IBS = 0.048) and machine learning (Random Survival Forest (RSF): C-index = 0.641, IBS = 0.048) models. The risk scores generated by the DL models also demonstrated superior performance. Moreover, AI models (NMTLR, DeepSurv, and RSF) were more effective, requiring the treatment of only 9 to 10 patients to prevent one CVD event, compared to the conventional model requiring treatment of nearly four times higher number of patients (NNT = 38). In summary, AI models, particularly DL models, possess superior predictive capabilities that can enhance patient treatment in a more cost-effective manner. Nonetheless, AI tools should serve to complement and assist healthcare professionals, rather than supplant them. The DeepSurv model, selected due to its relatively superior performance, is deployed in the form of web application locally, and is accessible on GitHub ( https://github.com/Robidar/Chuchu_Depl ). Finally, as we have demonstrated the benefit of using AI for reassessment of an existing CVD risk score, we recommend other infamous risk scores undergo similar reassessment., Competing Interests: Declarations. Competing interest: The authors declare no competing interests., (© 2024. The Author(s), under exclusive licence to American Aging Association.)

Neuroimaging studies have reported the possibility of semantic neural decoding to identify specific semantic concepts from neural activity. This offers promise for brain-computer interfaces (BCIs) for communication. However, translating these findings into a BCI paradigm has proven challenging. Existing EEG-based semantic decoding studies often rely on neural activity recorded when a cue is present, raising concerns about decoding reliability. To address this, we investigate the effects of cue presentation on EEG-based semantic decoding. In an experiment with a clear separation between cue presentation and mental task periods, we attempt to differentiate between semantic categories of animals and tools in four mental tasks. By using state-of-the-art decoding analyses, we demonstrate significant mean classification accuracies up to 71.3% during cue presentation but not during mental tasks, even with adapted analyses from previous studies. These findings highlight a potential issue when using neural activity recorded during cue presentation periods for semantic decoding. Additionally, our results show that semantic decoding without external cues may be more challenging than current state-of-the-art research suggests. By bringing attention to these issues, we aim to stimulate discussion and drive advancements in the field toward more effective semantic BCI applications., Competing Interests: Declarations Competing interests The authors declare no competing interests., (© 2024. The Author(s).)

Catalytic asymmetric hydrogenation of ketones is an important approach to prepare valuable chiral alcohols. Understanding how transition metals promote these reactions is key to the rational design of more active, selective and sustainable catalysts. A highly unusual mechanism for asymmetric hydrogenation of acetophenone catalysed by an anionic Ir III hydride system, including a strong counterion dependence on catalyst activity, is explored and rationalised here. The active catalyst, generated in situ from [IrCl(COD)] 2 and a bidentate ligand (P,S R ) under H 2 in the presence of a strong base (M +i PrO - in isopropanol, M = Li, Na, K), is the solvated M + [Ir(H) 4 (P,S R )] salt (P,S R = CpFe[1,2-C 5 H 3 (PPh 2 )(CH 2 S R )], with R = i Pr, Ph, Bz and Cy). Catalyst activity increases, for all R derivatives, significantly as the counterion is varied in the order Li < Na < K. For the most active K system, the addition of 18-crown-6 drastically reduces the activity. While the cation strongly affects catalyst activity, it does not significantly affect enantioselectivity. DFT calculations explored these effects in detail and showed that the solvation model used in the calculations is critical. Only a hybrid implicit/explicit solvent model including sufficient explicit solvent molecules to properly describe the first solvation shell of the cation is able to reproduce the experimental observations. This model revealed the fundamental importance of the alkali-metal cation coordination sphere in understanding the counterion effects. The turnover-determining states in the catalytic cycle are those involved in outer-sphere hydride transfer to the substrate. This step leads to coordination of the alkoxide product to the alkali-metal cation, with a significant rearrangement of the coordination sphere of M, whereas there is little change in the geometrical parameters around Ir or the alkoxide. The DFT calculations also pinpointed the major enantio-discriminating interactions and rationalised the insensitivity of the enantioselectivity on the alkali metal cation placement., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Link worker social prescribing programs are gaining recognition in Australia for addressing health and social needs outside routine medical care. The evaluation of these programs is essential for informing future social prescribing programs, research and evolving policy. However, diverse outcome evaluation measures present challenges for benchmarking across link worker social prescribing programs. An integrative review was conducted to identify and describe outcome domains and measures, and the methodological approaches and evaluation designs of link worker social prescribing programs in Australia. Comprehensive searches of the literature on link worker social prescribing programs in Australia were conducted across 14 electronic databases. In order to reduce the risk of bias, study selection and data extraction were conducted independently by multiple authors, and included studies underwent quality and risk of bias assessment using the standardised Mixed Methods Appraisal Tool. Six studies met the inclusion criteria. Outcome domains were categorised into 'person-level', 'system-level' and 'program implementation' domains. Despite the variation in participant groups, the 'person-level' domains of global well-being and social well-being were consistently evaluated. While measurement tools varied significantly, the WHO Quality of Life Brief Assessment and short-form UCLA Loneliness Scale were most commonly applied. At the system level, health service utilisation was primarily evaluated. This integrative review reports on the current state of evidence in Australia, with the potential to track changes and trends over time. Developing a core outcome set, incorporating stakeholder and consumer contributions for benchmarking aligned with the healthcare landscape is recommended. The findings may guide the refining of social prescribing initiatives and future research, ensuring methodological robustness and alignment with individual and community needs., Competing Interests: The authors have declared that no competing interests exist., (Copyright: © 2024 Baker et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.)

Background: Gender influences cardiovascular disease (CVD) through norms, social relations, roles and behaviours. This study identified gender-specific aspects of socialisation associated with CVD., Methods: A longitudinal study was conducted, involving 9936 (5,231 women and 4705 men) initially healthy, community-dwelling Australians aged 70 years or more from the ASPirin in Reducing Events in the Elderly (ASPREE) study and ASPREE Longitudinal Study of Older Persons, with a median follow-up time of 6.4 years. Variable categorisation, variable selection (using machine learning (ML) models; Elastic Net and extreme gradient boosting) and Cox-regression were employed separately by binary gender to identity socialisation factors (n=25 considered) associated with CVD., Results: Different socialisation factors were identified using the ML models. In the Cox model, for both genders, being married/partnered was associated with a reduced risk of CVD (men: HR 0.76, 95% CI 0.60 to 0.96; women: HR 0.67, 95% CI 0.58 to 0.95). For men, having 3-8 relatives they felt close to and could call on for help (HR 0.76, 95% CI 0.58 to 0.99; reference <3 relatives), having 3-8 relatives they felt at ease talking with about private matters (HR 0.70, 95% CI 0.55 to 0.90; reference <3 relatives) or playing games such as chess or cards (HR 0.82, 95% CI 0.67 to 1.00) was associated with reduced risk of CVD. For women, living with others (HR 0.71, 95% CI 0.55 to 0.91) or having ≥3 friends they felt at ease talking with about private matters (HR 0.74, 95% CI 0.58 to 0.95; reference <3 friends) was associated with a lower risk of CVD., Conclusions: This study demonstrates the need to prioritise gender-specific social factors to improve cardiovascular health in older adults., Competing Interests: Competing interests: None declared., (© Author(s) (or their employer(s)) 2024. No commercial re-use. See rights and permissions. Published by BMJ.)

Background: Widowhood negatively affects trajectories of social isolation and loneliness. Given the inevitability of spousal bereavement for many, further investigation into potential modifiers of bereavement-related loneliness is warranted., Aim: To examine the moderating effects of social isolation, social support, sociodemographic, self-efficacy, health, and quality of life factors on changes in loneliness before and after widowhood., Methods: We analysed 19 waves of data from the Household, Income and Labour Dynamics in Australia (HILDA) Survey, comprising 749 widowed and 8,418 married individuals (comparison). Coarsened exact matching weights were applied, controlling for age and time trends. Local polynomial smoothed plots illustrated social health trajectories from three years before to three years after spousal death. All analyses were gender-stratified., Results: Low social isolation and higher social support did not prevent increased loneliness following widowhood. Men in major cities were less likely to experience reductions in social isolation during bereavement, despite being less socially-isolated at baseline than men in regional/remote areas. The bereavement-loneliness relationship was consistent across all subgroups. For men, this relationship was weakened by older age and being born in a non-English-speaking country, but strengthened by poverty and living in a regional/remote areas. For women, it was weakened by older age, and strengthened by factors such as being born in a non-English-speaking country, poverty, employment or volunteering, and having a long-term mental health condition., Conclusion: Loneliness is a common and potentially unavoidable experience during widowhood, highlighting the importance of screening by healthcare workers to improve wellbeing and prevent future mental health issues., Competing Interests: Declaration of competing interest None declared. The analysis and interpretation of data; the writing of the manuscript; and the decision to submit the manuscript for publication were solely at the discretion of the researchers, independent of HILDA, DSS and the funders., (Copyright © 2024. Published by Elsevier B.V.)

Design of catalysts for Ni-catalyzed olefin polymerization predominantly focuses on ligand design rather than the activation process when attempting to achieve a broader scope of polyolefin micro- and macrostructures. Air-stable alkyl-or aryl-functionalized Ni II precatalysts were designed which eliminate the need of in situ alkylating processes and are activated solely by halide abstraction to generate the cationic complex for olefin polymerization. These complexes represent an emerging class of olefin polymerization catalysts, enabling the study of various cocatalysts forming either inner- or outer-sphere ion pairs. It is demonstrated that an organoboron cocatalyst activation produces a well-defined ion pair, which in contrast to ill-defined organoaluminum cocatalysts, can directly activate the complex by halide abstraction to yield comparatively higher molecular weight homo/copolymers. Under high ethylene pressure, broader branching densities and the gradual incorporation of short-chain branches were achieved, circumventing the need for elaborate ligand design and copolymerization with α-olefins. The underlying chain-walking mechanism and ion pair interactions were further elucidated by DFT calculations. A phenyl group on the bridging carbon functioned as a rotational barrier, producing higher molecular weight polymers compared to methyl-substituted analogs. Here, we provide a perspective to manipulate the iminopyridyl Ni II system, leveraging ion pair interactions and ligand design to govern polyolefin molecular weights and microstructures., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Purpose: This study examined the impact of a 5-wk sprint interval training (SIT) intervention on time to task failure (TTF) during severe-intensity constant work rate (CWR) exercise, as well as in glycolytic enzymatic content and activity, and glycogen content., Methods: Fourteen active males were randomized into either a SIT group ( n = 8) composed of 15 SIT sessions over 5 wk, or a control group ( n = 6). At pretraining period, participants performed i) ramp incremental test to measure the cardiorespiratory function; ii) CWR cycling TTF at 150% of the power output (PO) at the respiratory compensation point (RCP-PO) with muscle biopsies at rest and immediately following task failure. After 5 wk, the same evaluations were repeated (i.e., exercise intensities matched to current training status), and an additional cycling CWR matched to pretraining 150% RCP-PO was performed only for TTF evaluation. The content and enzymatic activity of glycogen phosphorylase (GPhos), hexokinase (HK), phosphofructokinase (PFK), and lactate dehydrogenase (LDH), as well as the glycogen content, were analyzed. Content of monocarboxylate transporter isoform 4 (MCT4) and muscle buffering capacity were also measured., Results: Despite improvements in total work performed at CWR posttraining, no differences were observed for TTF. The GPhos, HK, PFK, and LDH content and activity, and glycogen content also improved after training only in the SIT group. Furthermore, the MCT4 concentrations and muscle buffering capacity were also improved only for the SIT group. However, no difference in glycogen depletion was observed between groups and time., Conclusions: Five weeks of SIT improved the glycolytic pathway parameters and total work performed; however, glycogen depletion was not altered during CWR severe-intensity exercise, and TTF remained similar., (Copyright © 2024 by the American College of Sports Medicine.)

Artificial intelligence (AI) based predictive models for early detection of cardiovascular disease (CVD) risk are increasingly being utilised. However, AI based risk prediction models that account for right-censored data have been overlooked. This systematic review (PROSPERO protocol CRD42023492655) includes 33 studies that utilised machine learning (ML) and deep learning (DL) models for survival outcome in CVD prediction. We provided details on the employed ML and DL models, eXplainable AI (XAI) techniques, and type of included variables, with a focus on social determinants of health (SDoH) and gender-stratification. Approximately half of the studies were published in 2023 with the majority from the United States. Random Survival Forest (RSF), Survival Gradient Boosting models, and Penalised Cox models were the most frequently employed ML models. DeepSurv was the most frequently employed DL model. DL models were better at predicting CVD outcomes than ML models. Permutation-based feature importance and Shapley values were the most utilised XAI methods for explaining AI models. Moreover, only one in five studies performed gender-stratification analysis and very few incorporate the wide range of SDoH factors in their prediction model. In conclusion, the evidence indicates that RSF and DeepSurv models are currently the optimal models for predicting CVD outcomes. This study also highlights the better predictive ability of DL survival models, compared to ML models. Future research should ensure the appropriate interpretation of AI models, accounting for SDoH, and gender stratification, as gender plays a significant role in CVD occurrence., (© 2024. The Author(s).)

Introduction: Poor social connection is considered a risk factor for dementia. Since socializing behaviors may cluster together or act compensatorily, we aimed to investigate social connection patterns and their association with dementia, for men and women separately., Methods: A total of 12,896 community-dwelling older adults (mean ± SD age: 75.2 ± 4.3 years, 54% women) without major cognitive impairment were included. Latent class analysis was conducted using 24 baseline social connection indicators. Cox proportional hazards regression was used to estimate the association between latent classes and incident dementia over 12 (median: 8.4) years follow-up., Results: Three distinct classes were identified in both genders: strong social connections with an intermediate friend-relative network (Class 1: men, 43.8%; women, 37.9%), weak social connections (Class 2: men, 29.6%; women, 27.4%), and strong social connections with a larger friend-relative network (Class 3: men, 26.6%; women, 34.7%). Compared to Class 1, men in Class 2 (HR: 1.38, 95% CI: 1.08-1.77) and women in Class 3 (HR: 1.27, 95% CI: 1.01-1.60) had an increased risk of dementia., Discussion: Dementia risk varies with different social connection patterns among older men and women., Highlights: Three distinct social connection patterns were identified based on 24 indicators. These patterns were related to dementia risk differently in men and women. In men, a weak social connection pattern was associated with a higher dementia risk. In women, a strong social connection with a relatively larger friend-relative network was associated with a greater dementia risk., (© 2024 The Author(s). Alzheimer's & Dementia published by Wiley Periodicals LLC on behalf of Alzheimer's Association.)

Objective: To investigate the association between oral health status and all-cause mortality in older adults using prospective cohort study design., Setting and Participants: In total, 12 809 adults aged ≥70 years (54.3% females) were participants of the ASPREE Longitudinal Study of Older Persons (ALSOP)., Methods: Participants self-reported the presence of natural teeth and oral health status. The association of self-reported oral health, edentulism and the integrative measure of the two with all-cause mortality were explored using the Cox-regression models adjusted for age, gender, socio-economic status, health-related behaviours, weight status, aspirin and polypharmacy. Hazard ratios (HRs) and 95% confidence intervals (CIs) were reported., Results: In total, 22.2% of participants reported edentulism and 13.8% had fair/poor oral health. After adjustment for confounders, risk of all-cause mortality was higher among those with edentulism (vs. no edentulism) HR (95% CI) 1.43 (1.18, 1.73); and those with edentulism and reporting poor/fair oral health HR (95% CI) 1.69 (1.02, 2.82), or with no edentulism but reporting poor/fair oral health HR (95% CI) 1.46 (1.19-1.80) vs. no edentulism and reporting good/very good/excellent oral health. No association was observed between self-reported oral health alone and all-cause mortality., Conclusions: The risk of all-cause mortality was 69% higher among older adults reporting both edentulism and poor/fair oral health compared with those with teeth and more favourable self-reported oral health. © 2023 Australian Dental Association., (© 2023 The Authors. Australian Dental Journal published by John Wiley & Sons Australia, Ltd on behalf of Australian Dental Association.)

Background: BIPCOM aims to (1) identify medical comorbidities in people with bipolar disorder (BD); (2) examine risk factors and clinical profiles of Medical Comorbidities (MC) in this clinical group, with a special focus on Metabolic Syndrome (MetS); (3) develop a Clinical Support Tool (CST) for the personalized management of BD and medical comorbidities., Methods: The BIPCOM project aims to investigate MC, specifically MetS, in individuals with BD using various approaches. Initially, prevalence rates, characteristics, genetic and non-genetic risk factors, and the natural progression of MetS among individuals with BD will be assessed by analysing Nordic registers, biobanks, and existing patient datasets from 11 European recruiting centres across 5 countries. Subsequently, a clinical study involving 400 participants from these sites will be conducted to examine the clinical profiles and incidence of specific MetS risk factors over 1 year. Baseline assessments, 1-year follow-ups, biomarker analyses, and physical activity measurements with wearable biosensors, and focus groups will be performed. Using this comprehensive data, a CST will be developed to enhance the prevention, early detection, and personalized treatment of MC in BD, by incorporating clinical, biological, sex and genetic information. This protocol will highlight the study's methodology., Discussion: BIPCOM's data collection will pave the way for tailored treatment and prevention approaches for individuals with BD. This approach has the potential to generate significant healthcare savings by preventing complications, hospitalizations, and emergency visits related to comorbidities and cardiovascular risks in BD. BIPCOM's data collection will enhance BD patient care through personalized strategies, resulting in improved quality of life and reduced costly interventions. The findings of the study will contribute to a better understanding of the relationship between medical comorbidities and BD, enabling accurate prediction and effective management of MetS and cardiovascular diseases., Trial Registration: ISRCTN68010602 at https://www.isrctn.com/ISRCTN68010602 . Registration date: 18/04/2023., (© 2024. The Author(s).)

Objectives: This study examines the gender-specific associations between a wide range of social activities and dementia risk., Methods: A prospective cohort study was conducted involving community-dwelling older Australians (≥70 years) without significant cognitive impairment at enrolment. During the first year of enrolment, we assessed 25 self-reported social activities covering various aspects, including support from relatives and friends, community participation, social interactions with surroundings, and loneliness. Dementia diagnosis followed DSM-IV criteria, adjudicated by an international expert panel. To estimate hazard ratios (HR) and 95% confidence intervals (CI) for associations between social activities and dementia, we performed Cox proportional hazards models, adjusting for age, educational attainment, baseline global cognition, and depressive symptoms., Results: Among 9,936 participants who completed all social activity questionnaires (median [IQR] age: 73.4 [71.6-77.1] years; 47.4% men), dementia was diagnosed in 3.8% of men (n = 181/4,705) and 2.6% of women (n = 138/5,231) over a median 6.4 years (IQR: 5.3-7.6, range: 0.2-10.1) follow-up. Gender-specific relationships emerged: caregiving for a person with illness/disability in women (HR: 0.65, 95% CI: 0.42-0.99), and having ≥9 relatives feeling close to call for help in men (HR: 0.56, 95% CI: 0.33-0.96; reference <9 relatives) were associated with reduced dementia risk. Unexpectedly, in women, having ≥5 friends with whom they felt comfortable discussing private matters were associated with a greater dementia risk (HR: 1.69, 95% CI: 1.10-2.59; reference ≤2 friends). Imputed models further identified that babysitting/childminding was associated with lower dementia risk in men (HR: 0.75, 95% CI: 0.56-0.99). No other social activities showed significant associations with dementia., Discussion: This study provides evidence of social activities influencing dementia risk. Further investigations are required to uncover the mechanisms driving these observed relationships., (© The Author(s) 2024. Published by Oxford University Press on behalf of The Gerontological Society of America.)

A new one-pot solvent-less reaction to convert benzylic, allylic, ferrocenyl or tertiary alcohols into S-thioesters, bench-stable and less odorous precursors of the corresponding thiols, which is based on reactions in neat thioacetic acid in the presence of tetrafluoroboric acid, is presented. Reaction monitoring by NMR and GC of the benzyl alcohol conversion indicated the intermediate formation of benzyl acetate and benzyl thionoacetate (PhCH 2 OC(S)CH 3 ) prior to the slower conversion to the final S-benzyl thioacetate product. Increasing the HBF 4 concentration enhanced the reaction rate, giving good to excellent yield (up to 99 %) for a large scope of alcohols. Control experiments, with support of DFT calculations, have revealed a thermodynamically favorable, though requiring HBF 4 -activation, disproportionation of CH 3 C(O)SH to CH 3 C(O)OH and CH 3 C(S)SH, the latter immediately decomposing to H 2 S and (MeC) 4 S 6 but also generating the hitherto unreported [MeC(O)C(Me)S] 2 (μ-S) 2 . Kinetic investigations demonstrated that the rate of benzyl alcohol conversion is second-order in [PhCH 2 OH] and second order in [HBF 4 ], while the rate of conversion of the benzyl acetate intermediate to S-benzyl thioacetate is second order in [PhCOOMe] and fourth order in [HBF 4 ]. The DFT calculations rationalize the need to two alcohol molecules and two protons to generate the reactive benzyl cation., (© 2023 Wiley-VCH GmbH.)

Introduction: Risk factors for cardiovascular disease (CVD) also increase the risk of dementia. However, whether commonly used CVD risk scores are associated with dementia risk in older adults who do not have a history of CVD, and potential gender differences in this association, remains unclear. The aim of this study was to determine whether CVD risk scores are prospectively associated with cognitive decline and dementia in initially healthy older men and women., Methods: A total of19,114 participants from a prospective cohort of individuals aged 65+ years without known CVD or dementia were recruited. The atherosclerotic cardiovascular disease risk score (ASCVDRS), Systematic Coronary Risk Evaluation 2-Older Persons (SCORE2-OP), and the Framingham risk score (FRS) were calculated at baseline. Risk of dementia (according to DSM-IV criteria) and cognitive decline (defined as a &gt;1.5 standard deviation decline in global cognition, episodic memory, psychomotor speed, or verbal fluency from the previous year) were assessed using hazard ratio., Results: Over a median follow-up of 6.4 years, 850 individuals developed dementia and 4,352 cognitive decline. Men and women in the highest ASCVDRS tertile had a 41% (95% CI 1.08, 1.85) and 45% (1.11, 1.89) increased risk of dementia compared to the lowest tertile, respectively. Likewise, men and women in the highest SCORE2-OP tertile had a 64% (1.24, 2.16) and 60% (1.22, 2.11) increased risk of dementia compared to the lowest tertile, respectively. Findings were similar, but the risk was slightly lesser when examining risk of cognitive decline for both ASCVDRS and SCORE2-OP. However, FRS was only associated with the risk of cognitive decline among women (highest vs. lowest tertiles: 1.13 [1.01-1.26])., Conclusion: These findings suggest the utility of the ASCVDRS and SCORE2-OP in clinical practice, to not only assess future risk of CVD, but also as potential early indicators of cognitive impairment, even in relatively healthy older men and women., (© 2023 The Author(s). Published by S. Karger AG, Basel.)

Background: Knowledge of stroke is essential to empower people to reduce their risk of these events. However, valid tools are required for accurate and reliable measurement of stroke knowledge. We aimed to systematically review contemporary stroke knowledge assessment tools and appraise their content validity, feasibility, and measurement properties., Methods: The protocol was registered in PROSPERO (CRD42023403566). Electronic databases (MEDLINE, PsycInfo, CINAHL, Embase, Scopus, Web of Science) were searched to identify published articles (1 January 2015-1 March 2023), in which stroke knowledge was assessed using a validated tool. Two reviewers independently screened titles and abstracts prior to undertaking full-text review. COnsensus-based Standards for the selection of health Measurement INstruments (COSMIN) methods guided the appraisal of content validity (relevance, comprehensiveness, comprehensibility), feasibility, and measurement properties., Results: After removing duplicates, the titles and abstracts of 718 articles were screened; 323 reviewed in full; with 42 included (N = 23 unique stroke knowledge tools). For content validity, all tools were relevant, two were comprehensive, and seven were comprehensible. Validation metrics were reported for internal consistency (n = 20 tools), construct validity (n = 17 tools), cross-cultural validity (n = 15 tools), responsiveness (n = 9 tools), reliability (n = 7 tools), structural validity (n = 3 tools), and measurement error (n = 1 tool). The Stroke Knowledge Test met all content validity criteria, with validation data for six measurement properties (n = 3 rated "Sufficient")., Conclusion: Assessment of stroke knowledge is not standardised and many tools lacked validated content or measurement properties. The Stroke Knowledge Test was the most comprehensive but requires updating and further validation for endorsement as a gold standard., (© 2023 The Author(s). Published by S. Karger AG, Basel.)

To realize the goal of a carbon-free energy economy, it is crucial to discover reactions that utilize sustainable resources as alternatives to fossil feedstocks. In this study, a well-defined, air-stable Cp*Co(III)-catalyst for transfer hydrogenation of quinoline derivatives and oxidative dehydrogenation of cyclic amines in water is developed. While the former reaction is promoted by formic acid as a transfer hydrogenation reagent, the latter is mediated by molecular oxygen as the sole oxidant. These processes provide new avenues for the investigation of air-stable cobalt catalysts for environmentally benign hydrogenation and dehydrogenation reactions.

Background: Stress can have adverse impacts on health, particularly when it is chronic or resulting from major adverse events. Our study investigated whether relatively common adverse events in older individuals were associated with an increased risk of death, as well as cause-specific death and potential gender differences., Methods: Participants were 12896 community-dwelling Australians aged ≥70 years at enrolment into the ASPREE (ASPirin in Reducing Events in the Elderly) study and without known life-limiting disease. A questionnaire administered in the year after enrolment, collected information on ten adverse events experienced in the past year. Mortality status was verified by multiple sources including health records and the National Death Index across a maximum of 10 years. Underlying causes of death were determined using clinical information by two adjudicators. Cox-proportional hazards regression models were used to estimate mortality risk., Results: Two of the ten adverse events were associated with an increased risk of mortality in fully adjusted models. A 69% increased risk of mortality was observed in participants who reported their spouse/partner had recently died (95% CI: 1.19-2.39, P < 0.01). Cancer-related but not cardiovascular deaths also increased. Participants with a seriously ill spouse/partner also had a 23% increased risk of mortality (HR: 1.23, 95% CI: 1.02-1.48, P = 0.03). There was a tendency for these associations to be stronger among men than women., Limitations: Perceived stress and cortisol were not measured, thus limiting our understanding of the psychological and physiological impacts of adverse events., Conclusions: Experiencing adverse events in later-life, especially the death of a spouse/partner, may be a risk factor for earlier mortality. These findings may increase public health awareness and better inform initiatives for particular groups, including bereaved men., Competing Interests: All authors declare that they have no conflicts of interest., (© 2023 The Authors.)

The solution behavior of complex [Rh(COD)(μ-OAc)] 2 in the absence and presence of PPN + OAc - in dichloromethane has been investigated in detail by multinuclear NMR spectroscopy. Without additional acetate ions, the compound shows dynamic behavior at room temperature, consistent with an inversion of its C 2 v structure. Addition of PPN + OAc - reveals an equilibrated generation of [Rh(COD)(OAc) 2 ] - . Rapid exchange is observed at room temperature between the neutral dimer and the anionic mononuclear complex, as well as between the anionic complex and free acetate. Lowering the temperature to 213 K freezes the exchange between the two Rh complexes, but fast exchange between the anionic Rh complex and free acetate maintains coalesced Me ( 1 H and 13 C) and COO ( 13 C) NMR resonances. DFT calculations support the experimental data and lean in favour of a dissociative mechanism for the acetate exchange in [Rh(COD)(OAc) 2 ] - . The acetate ligands in complex [Rh(COD)(μ-OAc)] 2 are also exchanged in a biphasic (water/organic) system with the methacrylic acid (MAA) functions of hydrosoluble [MMA 0.5 - co -PEOMA 0.5 ] 30 copolymer chains (PEOMA = poly(ethylene oxide) methyl ether methacrylate), resulting in transfer of the Rh complex to the aqueous phase. Exchange with the MAA functions in the same polymer equally takes place for the chloride ligands of [Rh(COD)(μ-Cl)] 2 . The latter phenomenon rationalizes the coagulation of a core-crosslinked micelle (CCM) latex, where MMA functions are present on the hydrophilic CCM shell, when a dichloromethane solution of [Rh(COD)(μ-Cl)] 2 is added.

Background: Cardiovascular disease (CVD) is the greatest contributor to global morbidity and mortality. Poor social health plays a critical role in CVD incidence. Additionally, the relationship between social health and CVD may be mediated through CVD risk factors. However, the underlying mechanisms between social health and CVD are poorly understood. Certain social health constructs (social isolation, low social support and loneliness) have complicated the characterisation of a causal relationship between social health and CVD., Aim: To provide an overview of the relationship between social health and CVD (and its shared risk factors)., Method: In this narrative review, we examined published literature on the relationship between three social health constructs (social isolation, social support, and loneliness) and CVD. Evidence was synthesised in a narrative format, focusing on the potential ways in which social health affects CVD, including shared risk factors., Results: The current literature highlights an established relationship between social health and CVD with a likelihood for bi-directionality. However, there is speculation and varied evidence regarding how these relationships may be mediated through CVD risk factors., Conclusions: Social health can be considered an established risk factor for CVD. However, the potential bi-directional pathways of social health with CVD risk factors are less established. Further research is needed to understand whether targeting certain constructs of social health may directly improve the management of CVD risk factors. Given the health and economic burdens of poor social health and CVD, improvements to addressing or preventing these interrelated health conditions would have societal benefits., Competing Interests: Declaration of Competing Interest Authors declare that they have no conflict of interest., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Cardiovascular disease (CVD) is the leading cause of mortality worldwide. Addressing social determinants of health (SDoH) may be the next forefront of reducing the enormous burden of CVD. SDoH can be defined as any social, economic, or environmental factor that influences a health outcome. Comprehensive evidence of the role of SDoH in CVD is lacking, nevertheless. This umbrella review aims to give a comprehensive overview of the role of SDoH in CVD. We searched systematic reviews (with or without meta-analyses) using 8 databases and included review reference lists. Four themes (economic circumstances, social/community context, early childhood development, and neighbourhood/built environment) and health literacy in the health/health care theme were considered. Seventy reviews were eligible. Despite the quality of the included reviews being low or critically low, there was consistent evidence that factors relating to economic circumstances and early childhood development themes were associated with an increased risk of CVD and CVD mortality. We also found evidence that factors in the social/community context and neighbourhood/built environment themes, such as social isolation, fewer social roles, loneliness, discrimination, ethnicity, neighborhood socioeconomic status, violence, and environmental attributes, had a role in CVD. SDoH factors without (or with minimal) evidence synthesis for CVD were also identified. In sum, this umbrella review offers evidence that SDoH, especially economic circumstance and early childhood development, play a significant role in CVD. This calls for the strengthening of nonmedical interventions that address multiple factors simultaneously and the inclusion of SDoH in future CVD risk prediction models. Registration URL: https://www.crd.york.ac.uk/prospero/; Unique identifier: CRD42022346994.

The kinetics and mechanism of the acetate ligand exchange with free acetic acid in [Zr 6 O 4 (OH) 4 (O 2 CCH 3 ) 12 ] 2 , used as a molecular model of crosslink migration in [Zr 6 O 4 (OH) 4 (carboxylate) 12- n (OH) n ]-based coordination adaptable networks with vitrimer-like properties, has been thoroughly investigated by dynamic 1 H NMR and DFT calculations. The compound maintains its C 2h -symmetric Zr 12 structure in CD 2 Cl 2 and C 6 D 6 , while it splits into its Zr 6 subunits in CD 3 OD and D 2 O. In the Zr 12 structure, the topologically different acetates (3 chelating, 6 belt-bridging, 2 intercluster-bridging and 1 inner-face-bridging) of the Zr 6 subunits behave differently in the presence of free CH 3 COOH: very fast exchange for the chelating (coalesced resonance at room temperature), slower exchange for the belt-bridging (line broadening upon warming), no observable exchange up to 65 °C (by EXSY NMR) for the intercluster- and inner-face-bridging. The rates of the first two exchange processes have zero-order dependence on [CH 3 COOH]. Variable-temperature line broadening studies yielded Δ H ‡ = 15.0 ± 0.4 kcal mol -1 , Δ S ‡ = 8 ± 1 cal mol -1 K -1 (-30 to +25 °C range in CD 2 Cl 2 ) for the chelating acetates and Δ H ‡ = 22.7 ± 1.6, 22.9 ± 2.1 and 20.6 ± 1.0 kcal mol -1 and Δ S ‡ = 13 ± 5, 14 ± 6 and 9 ± 3 cal mol -1 K -1 , respectively (+25 to +70 °C range in C 6 D 6 ), for three distinct resonances of magnetically inequivalent belt-bridging acetates. With support of DFT calculations, these results point to an operationally associative mechanism involving a rate-determining partial dissociation to monodentate acetate, followed by rapid acid coordination and proton transfer. The cluster μ 3 -OH ligands accelerate the exchange processes through H-bonding stabilization of the coordinatively unsaturated intermediate. The lower exchange barrier for the chelated vs. bridging acetates is associated to the release of ring strain. The results presented in this investigation may help the interpretation of carboxylate exchange phenomena in other systems and the design of new carboxylate-based materials., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Over the last century, the number of epidemics caused by RNA viruses has increased and the current SARS-CoV-2 pandemic has taught us about the compelling need for ready-to-use broad-spectrum antivirals. In this scenario, natural products stand out as a major historical source of drugs. We analyzed the antiviral effect of 4 stilbene dimers [1 (trans-δ-viniferin); 2 (11',13'-di-O-methyl-trans-δ-viniferin), 3 (11,13-di-O-methyl-trans-δ-viniferin); and 4 (11,13,11',13'-tetra-O-methyl-trans-δ-viniferin)] obtained from plant substrates using chemoenzymatic synthesis against a panel of enveloped viruses. We report that compounds 2 and 3 display a broad-spectrum antiviral activity, being able to effectively inhibit several strains of Influenza Viruses (IV), SARS-CoV-2 Delta and, to some extent, Herpes Simplex Virus 2 (HSV-2). Interestingly, the mechanism of action differs for each virus. We observed both a direct virucidal and a cell-mediated effect against IV, with a high barrier to antiviral resistance; a restricted cell-mediated mechanism of action against SARS-CoV-2 Delta and a direct virustatic activity against HSV-2. Of note, while the effect was lost against IV in tissue culture models of human airway epithelia, the antiviral activity was confirmed in this relevant model for SARS-CoV-2 Delta. Our results suggest that stilbene dimer derivatives are good candidate models for the treatment of enveloped virus infections., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Masson SAS.)

Background: Increasing evidence suggests that stress could be a risk factor for dementia but this might vary by gender. This study investigated whether adverse life events were associated with cognitive decline and dementia in later-life, separately in men and women., Methods: Participants were 12,789 community-dwelling Australians aged ≥ 70 years. Ten common adverse events in later-life were self-reported. Cognitive decline was defined as a 1.5 SD decline from participants' baseline score in tests of global cognition, psychomotor speed, episodic memory, and executive functioning, which were assessed regularly over a maximum of 10.3 years. Dementia was diagnosed according to DSM-IV criteria., Results: An increased risk of dementia was observed in participants who experienced the death of a spouse/partner (HR: 1.72, 95% CI: 1.17 - 2.52) and for individuals who experienced major financial problems (HR: 1.53, 95% CI: 1.05 - 2.23). The latter also increased the risk of cognitive decline in men specifically (HR: 1.43, 95% CI: 1.10 - 1.86). In contrast, some events for women were associated with a reduced risk of dementia (e.g. close family or friends lost their job/retired (HR: 0.62, 95% CI: 0.40-0.95))., Limitations: Events including major money problems may result from prodromal dementia symptoms, thus reverse causation needs to be considered., Conclusions: Adverse life events may influence dementia risk in older adults, but associations vary depending on the nature of the event, and across genders. These findings support the need for early interventions in older people who have experienced adversities, particularly for the death of a loved one., Competing Interests: Declaration of Competing Interest All authors declare that they have no conflicts of interest.

Objective: To identify the socio-demographic, lifestyle, and clinical characteristics associated with self-reported weight status in early (age 18 years) and late (age ≥ 70 years) adulthood., Methods: The number of participants was 11,288, who were relatively healthy community-dwelling Australian adults aged ≥70 years (mean age 75.1 ± 4.2 years) in the Aspirin in Reducing Events in the Elderly (ASPREE) Longitudinal Study of Older Persons (ALSOP) sub-study. Self-reported weight at the study baseline (age ≥ 70 years) and recalled weight at age 18 years were collected. Height measured at baseline was used to calculate the BMI at both time points. Individuals were categorised into one of five 'lifetime' weight status groups: healthy weight (at both age 18 year and ≥70 years), overweight (at either or both times), non-obese (age 18 year) to obesity (age ≥70 years), obesity (age 18 years) to non-obese (age ≥ 70 years), and early and later life obesity (at age 18 years and ≥70 years)., Results: Participants who experienced obesity in early and/or late adulthood were at a higher risk of adverse clinical characteristics. Obesity in late adulthood (regardless of early adulthood weight status) was associated with high proportions of hypertension, diabetes, and dyslipidaemia, whereas obesity in early adulthood (regardless of late adulthood weight status) was associated with lower cognitive scores (on all four measures)., Discussion/conclusion: Healthy or overweight weight status in early and later adulthood was associated with more favourable socioeconomic, lifestyle, and clinical measures. Obesity in early adulthood was associated with lower cognitive function in later adulthood, whereas obesity in later adulthood was associated with hypertension, diabetes, and dyslipidaemia.

Background: There is a complete lack of studies focusing on the association between care degree (reflecting the long-term care need) and loneliness or social isolation in Germany., Aims: To investigate the association between care degree and loneliness as well as perceived social isolation during the COVID-19 pandemic., Methods: We used data from the nationally representative German Ageing Survey, which covers community-dwelling middle-aged and older individuals aged 40 years or over. We used wave 8 of the German Ageing Survey (analytical sample: n = 4334 individuals, mean age was 68.9 years, SD: 10.2 years; range 46-100 years). To assess loneliness, the De Jong Gierveld instrument was used. To assess perceived social isolation, the Bude and Lantermann instrument was used. Moreover, the level of care was used as a key independent variable (absence of care degree (0); care degree 1-5)., Results: After adjusting for various covariates, regressions showed that there were no significant differences between individuals without a care degree and individuals with a care degree of 1 or 2 in terms of loneliness and perceived social isolation. In contrast, individuals with a care degree of 3 or 4 had higher loneliness (β = 0.23, p = 0.034) and higher perceived social isolation scores (β = 0.38, p < 0.01) compared to individuals without a care degree., Discussion/conclusions: Care degrees of 3 or 4 are associated with higher levels of both loneliness and perceived social isolation. Longitudinal studies are required to confirm this association., (© 2023. The Author(s).)

The addition of benzoyl peroxide to [Co II (acac) 2 ] in a 1 : 2 ratio selectively produces [Co III (acac) 2 (O 2 CPh)], a diamagnetic (NMR) mononuclear Co III complex with an octahedral (X-ray diffraction) coordination geometry. It is the first reported mononuclear Co III derivative with a chelated monocarboxylate ligand and an entirely O-based coordination sphere. The compound degrades in solution quite slowly by homolytic Co III -O 2 CPh bond cleavage upon warming above 40 °C to produce benzoate radicals and can serve as a unimolecular thermal initiator for the well-controlled radical polymerisation of vinyl acetate. Addition of ligands (L = py, NEt 3 ) induces benzoate chelate ring opening and formation of both cis and trans isomers of [Co III (acac) 2 (O 2 CPh)(L)] for L = py under kinetic control, then converting quantitatively to the cis isomer, whereas the reaction is less selective and equilibrated for L = NEt 3 . The py addition strengthens the Co III -O 2 CPh bond and lowers the initiator efficiency in radical polymerisation, whereas the NEt 3 addition results in benzoate radical quenching by a redox process. In addition to clarifying the mechanism of the radical polymerisation redox initiation by peroxides and rationalizing the quite low efficiency factor for the previously reported [Co II (acac) 2 ]/peroxide-initiated organometallic-mediated radical polymerisation (OMRP) of vinyl acetate, this investigation provides relevant information on the Co III -O homolytic bond cleavage process.

Background: Posttraumatic Stress Disorder (PTSD) could potentially increase the risk of mortality, and there is a need for a meta-analysis to quantify this association. This study aims to determine the extent to which PTSD is a predictor of mortality., Methods: EMBASE, MEDLINE, and PsycINFO were searched systematically on 12th February 2020, with updated searches conducted in July 2021, and December 2022 (PROSPERO CRD42019142971). Studies involving community-dwelling participants with a diagnosis of PTSD or PTSD symptoms, and a comparator group of individuals without PTSD, and which assessed mortality risk, were included. A random-effects meta-analysis was conducted on studies reporting Odds Ratio (OR), Hazard Ratio (HR), and Risk Ratio (RR), and subgroup analysis was also performed by age, sex, type of trauma experienced, PTSD diagnosis, and cause of death., Results: A total of 30 eligible studies of mostly good methodological quality were identified, with a total of more than 2.1 million participants with PTSD. The majority of studies involved male-dominated, veteran populations. PTSD was associated with a 47% (95% CI: 1.06-2.04) greater risk of mortality across six studies that reported OR/RR, and a 32% increased risk across 18 studies which reported time to death (HR: 1.32, 95% CI: 1.10-1.59). There was very high study heterogeneity (I 2  > 94%) and this was not explained by the prespecified subgroup analysis., Conclusion: PTSD is associated with increased mortality risk, however further research is required amongst civilians, involving women, and in individuals from underdeveloped countries., (© 2023. The Author(s).)

Thia-Michael additions (1,4-additions of a thiol to a Michael acceptor) are generally catalyzed by an external Brønsted or Lewis base. A spontaneous (uncatalyzed) Michael addition of thiols to α-trifluoromethyl acrylates is described, as well as its application to the very efficient preparation of a thermoset. A thorough mechanistic investigation, based on an experimental kinetic study and on DFT calculations, is presented for the addition of arene- and alkanethiols to tert-butyl trifluoromethyl acrylate in polar aprotic solvents, unveiling a probable solvent-assisted proton transfer in the rate-determining step and a considerable lowering of the energy barrier induced by the CF 3 group., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Background: Social prescribing (SP) enables healthcare professionals to link patients with non-medical interventions available in the community to address underlying socioeconomic and behavioural determinants. We synthesised the evidence to understand the effectiveness of SP for chronic disease prevention., Methods: A systematic literature search was conducted using five databases and two registries. Eligible studies included randomised controlled trials of SP among community-dwelling adults recruited from primary care or community setting, investigating any chronic disease risk factors defined by the WHO (behavioural factors: smoking, physical inactivity, unhealthy diet and excessive alcohol consumption; metabolic factors: raised blood pressure, overweight/obesity, hyperlipidaemia and hyperglycaemia). Random effect meta-analyses were performed at two time points: completion of intervention and follow-up after trial., Results: We identified nine reports from eight trials totalling 4621 participants. All studies evaluated SP exercise interventions which were highly heterogeneous regarding the content, duration, frequency and length of follow-up. Majority of studies had some concerns for risk of bias. Meta-analysis revealed that SP likely increased physical activity (completion: mean difference (MD) 21 min/week, 95% CI 3 to 39, I 2 =0%; follow-up ≤12 months: MD 19 min/week, 95% CI 8 to 29, I 2 =0%). However, SP may not improve markers of adiposity, blood pressure, glucose and serum lipid. There were no eligible studies that primarily target unhealthy diet, smoking and excessive alcohol drinking behaviours., Conclusions: SP exercise interventions probably increased physical activity slightly; however, no benefits were observed for metabolic factors. Determining whether SP is effective in modifying the determinants of chronic diseases and promotes sustainable healthy behaviours is limited by the current evidence of quantification and uncertainty, warranting further rigorous studies., Prospero Registration Number: CRD42022346687., Competing Interests: Competing interests: None declared., (© Author(s) (or their employer(s)) 2023. No commercial re-use. See rights and permissions. Published by BMJ.)

Both cardiovascular disease (CVD) and social health carry high health and economic burdens. We undertook a systematic review to investigate the association between social isolation, low social support, and loneliness with health service utilisation and survival after a CVD event among people living in Australia and New Zealand. Four electronic databases were systematically searched for the period before June 2020. Two reviewers undertook the title/abstract screen. One reviewer undertook a full-text screen and data extraction. A second author checked data extraction. Of 756 records, 25 papers met our inclusion criteria. Included studies recruited 10-12,821 participants, aged 18-98 years, and the majority were males. Greater social support was consistently associated with better outcomes on four of the five themes (discharge destination, outpatient rehabilitation attendance, rehospitalisation and survival outcomes; no papers assessed the length of inpatient stay). Positive social health was consistently associated with better discharge designation to higher independent living. As partner status and living status did not align with social isolation and social support findings in this review, we recommend they not be used as social health proxies. Our systematic review demonstrates that social health is considered in cardiac care decisions and plays a role in how healthcare is being delivered (i.e., outpatient, rehabilitation, or nursing home). This likely contributes to our finding that lower social support is associated with high-intensity healthcare services, lower outpatient rehabilitation attendance, greater rehospitalisation and poorer survival. Given our evidence, the first step to improve cardiac outcomes is acknowledging that social health is part of the decision-making process. Incorporating a formal assessment of social support into healthcare management plans will likely improve cardiac outcomes and survival. Further research is required to assess if support person/s need to engage in the risk reduction behaviours themselves for outpatient rehabilitation to be effective. Further synthesis of the impact of social isolation and loneliness on health service utilisation and survival after a CVD event is required.

Background: Psychological distress (stress) has been linked to an increased risk of chronic diseases and is exacerbated by a range of workplace factors. Physical activity has been shown to alleviate psychological distress. Previous pedometer-based intervention evaluations have tended to focus on physical health outcomes. This study aimed to investigate the immediate and long-term changes in psychological distress in employees based in Melbourne, Australia after their participation in a four-month pedometer-based program in sedentary workplaces., Methods: At baseline, 716 adults (aged 40 ± 10 years, 40% male) employed in primarily sedentary occupations, voluntarily enrolled in the Global Corporate Challenge© (GCC©), recruited from 10 Australian workplaces to participate in the GCC ® Evaluation Study, completed the Kessler 10 Psychological Distress Scale (K10). Of these, 422 completed the K10 at baseline, 4 months and 12 months., Results: Psychological distress reduced after participation in a four-month workplace pedometer-based program, which was sustained eight months after the program ended. Participants achieving the program goal of 10,000 steps per day or with higher baseline psychological distress had the greatest immediate and sustained reductions in psychological distress. Demographic predictors of immediate reduced psychological distress (n = 489) was having an associate professional occupation, younger age, and being 'widowed, separated or divorced'., Conclusions: Participation in a workplace pedometer-based program is associated with a sustained reduction in psychological distress. Low-impact physical health programs conducted in groups or teams that integrate a social component may be an avenue to improve both physical and psychological health in the workplace.

The reaction between [IrCl(COD)] 2 and dppe in a 1 : 2 ratio was investigated in detail under three different conditions. [IrCl(COD)(dppe)], 1, is formed at room temperature in the absence of base. In the presence of a strong base at room temperature, hydride complexes that retain the carbocyclic ligand in the coordination sphere are generated. In isopropanol, 1 is converted into [IrH(1,2,5,6-η 2 :η 2 -COD)(dppe)] (2) on addition of KO t Bu, with k 12 = (1.11 ± 0.02) × 10 -4 s -1 , followed by reversible isomerisation to [IrH(1-κ-4,5,6-η 3 -C 8 H 12 )(dppe)] (3) with k 23 = (3.4 ± 0.2) × 10 -4 s -1 and k 32 = (1.1 ± 0.3) × 10 -5 s -1 to yield an equilibrium 5 : 95 mixture of 2 and 3. However, when no hydride source is present in the strong base (KO t Bu in benzene or toluene), the COD ligand in 1 is deprotonated, followed by β-H elimination of an Ir I -C 8 H 11 intermediate, which leads to complex [IrH(1-κ-4,5,6-η 3 -C 8 H 10 )(dppe)] (4) selectively. This is followed by its reversible isomerisation to 5, which features a different relative orientation of the same ligands ( k 45 = (3.92 ± 0.11) × 10 -4 s -1 ; k 5-4 = (1.39 ± 0.12) × 10 -4 s -1 in C 6 D 6 ), to yield an equilibrated 32 : 68 mixture of 4 and 5. DFT calculations assisted in the full rationalization of the selectivity and mechanism of the reactions, yielding thermodynamic (equilibrium) and kinetic (isomerization barriers) parameters in excellent agreement with the experimental values. Finally, in the presence of KO t Bu and isopropanol at 80 °C, 1 is transformed selectively to K[IrH 4 (dppe)] (6), a salt of an anionic tetrahydride complex of Ir III . This product is also selectively generated from 2, 3, 4 and 5 and H 2 at room temperature, but only when a strong base is present. These results provide an insight into the catalytic action of [IrCl(COD)(LL)] complexes in the hydrogenation of polar substrates in the presence of a base.

Background: Optimism is a disposition characterised by positive future expectancies, while pessimism is characterised by expecting the worst. High optimism and low pessimism promote the health of older adults and may potentiate full engagement in life. We identified socioeconomic, behavioural, and social factors associated with optimism and pessimism in older adults., Methods: Participants included 10,146 community-dwelling, apparently healthy Australian adults aged 70 years and over from the ASPREE Longitudinal Study of Older Persons (ALSOP). Optimism and pessimism were measured using the revised Life Orientation Test. Cross-sectional ordinal logistic regression was used to determine the socioeconomic, behavioural, and social health factors associated with optimism and pessimism., Results: Higher education, greater physical activity, lower loneliness, and volunteering were associated with higher optimism and lower pessimism. Low social support was associated with higher pessimism. Higher socioeconomic advantage, greater income, and living alone were associated with lower pessimism. Women were more optimistic and less pessimistic than men. The association of age, smoking status, and alcohol consumption with optimism and pessimism differed for men and women., Conclusions: Factors associated with higher optimism and lower pessimism were also those demonstrated to support healthy ageing. Health-promotion action at the individual level (e.g., smoking cessation or regular physical activity), health professional level (e.g., social prescribing or improving access and quality of care for all older adults), and community level (e.g., opportunities for volunteer work or low-cost social activities for older adults) may improve optimism and reduce pessimism, possibly also promoting healthy ageing.

Background: Gerontology and ageing research are increasingly focussing on healthy life span (healthspan), the period of life lived free of serious disease and disability. Late-life depression (LLD) is believed to impact adversely on physical health. However, no studies have examined its effect on healthspan. This study investigated the effect of LLD and subthreshold depression on disability-free survival, a widely accepted measure of healthspan., Methods: This prospective cohort study used data from the ASPirin in Reducing Events in the Elderly study. Participants were aged ≥70 years (or ≥65 years for African-American and Hispanic participants) and free of dementia, physical disability and cardiovascular disease. Depressive symptoms were measured using the 10-item Centre for Epidemiological Studies Depression Scale (CES-D-10). LLD and subthreshold depression were defined as CES-D-10 scores ≥8 and 3-7, respectively. Disability-free survival was defined as survival free of dementia and persistent physical disability., Results: A total of 19,110 participants were followed up for a maximum of 7.3 years. In female participants, LLD was associated with lower disability-free survival adjusting for sociodemographic and lifestyle factors, medical comorbidities, polypharmacy, physical function and antidepressant use (HR, 1.50; 95% CI, 1.23-1.82). In male participants, LLD was associated with lower disability-free survival adjusting for sociodemographic and lifestyle factors (HR, 1.30; 95% CI, 1.03-1.64). Subthreshold depression was also associated with lower disability-free survival in both sexes., Conclusions: LLD may be a common and important risk factor for shortened healthspan., (© 2022 The Authors. Acta Psychiatrica Scandinavica published by John Wiley & Sons Ltd.)

Objectives: The extent to which body weight in early adulthood is associated with late-life mortality risk is unclear. This study aimed to determine the association between body mass index (BMI) in early adulthood (at 18 years of age) and older age (70 years and over), and the risk of mortality in later life., Design: Secondary analysis of the ASPREE Longitudinal Study of Older Persons (ALSOP)., Setting, Participants: Data were from 14,853 relatively healthy community-dwelling Australians aged ≥ 70 years when enrolled in the study., Measurements: Self-reported weight at age ≥ 70 years and recalled weight at age 18 years were collected at ALSOP study baseline. Height was measured with a stadiometer and was used for calculation of BMI at both timepoints. BMI at each timepoint was defined as: underweight, normal weight, overweight and obese. Individuals were categorised into one of five 'lifetime' BMI groups: normal weight (BMI between 18.5 and 24.9 at both times), overweight (25.0-29.9 at either or both times), obesity to non-obese (≥30.0 at age 18 and <30.0 ≥ 70 years), non-obese to obesity (<30.0 at age 18 and ≥30.0 at age ≥ 70 years), and early and later life obesity (≥30.0 at both times)., Results: During a median 4.7 years follow-up, 715 deaths occurred. Obesity at 18 years, but not in older age (p=0.44), was significantly associated with the risk of mortality in later life, even after accounting for current health status (HR: 2.35, 95% CI: 1.53-3.58, p<0.001). Compared with participants with normal BMI at both time points, being obese at both time points was associated with increased mortality risk (HR=1.99, 95% CI: 1.04-3.81, p=0.03), and the risk was even greater for individuals who were obese at 18 years but were no longer obese in older age (HR=2.92, 95% CI: 1.65-5.16, p<0.001), in fully adjusted models. Participants who were normal weight at 18 years and were obese in later life, did not have an increased mortality risk (p=0.78)., Conclusions: Obesity in early adulthood, and obesity in both early and later life, were associated with increased mortality risk in later life. This highlights the importance of preventing obesity in early adulthood and maintaining a normal weight over an adult lifespan., Competing Interests: The authors have no conflicts of interest to declare.

Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.

Stable latexes containing unimolecular amphiphilic core-shell star-block polymers with a triphenylphosphine(TPP)-functionalized hydrophobic core and an outer hydrophilic shell based on anionic styrenesulfonate monomers have been synthesized in a convergent three-step strategy by reversible addition-fragmentation chain-transfer (RAFT) polymerization, loaded with [RhCl(COD)] 2 and applied to the aqueous biphasic hydrogenation of styrene. When the outer shell contains sodium styrenesulfonate homopolymer blocks, treatment with a toluene solution of [RhCl(COD)] 2 led to undesired polymer coagulation. Investigation of the interactions of [RhCl(COD)] 2 and [RhCl(COD)(PPh 3 )] with smaller structural models of the polymer shell functions, namely sodium p -toluenesulfonate, sodium styrenesulfonate, and a poly(sodium styrenesulfonate) homopolymer in a biphasic toluene/water medium points to the presence of equilibrated Rh-sulfonate interactions as the cause of coagulation by inter-particle cross-linking. Modification of the hydrophilic shell to a statistical copolymer of sodium styrenesulfonate and poly(ethylene oxide) methyl ether methacrylate (PEOMA) in a 20:80 ratio allowed particle loading with the generation of core-anchored [RhCl(COD)TPP] complexes. These Rh-loaded latexes efficiently catalyze the aqueous biphasic hydrogenation of neat styrene as a benchmark reaction. The catalytic phase could be recovered and recycled, although the performances in terms of catalyst leaching and activity evolution during recycles are inferior to those of equivalent nanoreactors based on neutral or polycationic outer shells.

Vitrimers are 3D "covalent adaptable networks" (CANs) with flow properties thanks to thermally activated associative exchange reactions. This contribution introduces coordination adaptable networks, or CooANs, that are topologically related to metal-organic frameworks with octahedral Zr 6 clusters as secondary building units in a carboxylic acid-functionalized acrylate-methacrylate copolymer matrix. A series of Zr-CooAN-x materials (x=percent of Zr 6 loading relative to maximum capacity) was synthesized with x=5, 10, 15, 20, 25, 50 and 100. The mechanical and rheological investigations demonstrate vitrimer-like properties for x up to 50, the crosslink migration being ensured by carboxylate ligand exchange, with relaxation becoming slower as the Zr 6 content is increased. The flow activation energy of Zr-CooAN-10 is 92.9±3.6 kJ mol -1 . Rapid (30 min) hot-press reshaping occurs at temperatures in the 50-100 °C range under a 3-ton pressure and does not significantly alter the material properties., (© 2022 Wiley-VCH GmbH.)

Background: An international systematic review concluded that individuals with poor social health (social isolation, lack of social support or loneliness) are 30% more likely to develop coronary heart disease (CHD) and stroke. Notably, the two included Australian papers reported no association between social health and CHD or stroke., Objective: We undertook a systematic review and meta-analysis to investigate the association between social isolation, lack of social support and loneliness and cardiovascular disease (CVD) incidence among people living in Australia and New Zealand., Methods: Four electronic databases were systematically searched for longitudinal studies published until June 2020. Two reviewers undertook title/abstract screen and one reviewer undertook full-text screen and data extraction. Quality was assessed using the Newcastle - Ottawa Quality Assessment Scale., Results: Of the 725 unique records retrieved, five papers met our inclusion criteria. These papers reported data from three Australian longitudinal datasets, with a total of 2137 CHD and 590 stroke events recorded over follow-up periods ranging from 3 to 16 years. Reports of two CHD and two stroke outcomes were suitable for meta-analysis. The included papers reported no association between social health and incidence of CVD in all fully adjusted models and most unadjusted models., Conclusions: Our systematic review is inconclusive as it identified only a few studies, which relied heavily on self-reported CVD. Further studies using medical diagnosis of CVD, and assessing the potential influence of residential remoteness, are needed to better understand the relationship between social health and CVD incidence in Australia and New Zealand., (© 2022 The Authors. Health Promotion Journal of Australia published by John Wiley & Sons Australia, Ltd on behalf of Australian Health Promotion Association.)

Objective: Positive psychosocial factors may protect against cardiovascular disease (CVD). We aimed to determine the association of optimism and pessimism with CVD events in community-dwelling older adults. Methods: 11,651 adults aged 70 years and over, participants of the ASPREE Longitudinal Study of Older Persons (ALSOP), were followed-up for 4.7 years (median). The association of optimism and pessimism (assessed as separate constructs by revised Life Orientation Test) and incident CVD events (composite and components) was assessed by Cox regression adjusted for demographic, socioeconomic and health factors. Results: No association was observed between optimism and pessimism with composite CVD events. Being more pessimistic was associated with a greater risk of fatal coronary heart disease, while being more optimistic was associated with a lower risk of non-fatal myocardial infarction. Conclusions: Optimism and pessimism may shape cardiovascular health of older adults; and we argue these psychosocial factors should be researched as separate constructs.

The vanishing gradient problem (i.e., gradients prematurely becoming extremely small during training, thereby effectively preventing a network from learning) is a long-standing obstacle to the training of deep neural networks using sigmoid activation functions when using the standard back-propagation algorithm. In this paper, we found that an important contributor to the problem is weight initialization. We started by developing a simple theoretical model showing how the expected value of gradients is affected by the mean of the initial weights. We then developed a second theoretical model that allowed us to identify a sufficient condition for the vanishing gradient problem to occur. Using these theories we found that initial back-propagation gradients do not vanish if the mean of the initial weights is negative and inversely proportional to the number of neurons in a layer. Numerous experiments with networks with 10 and 15 hidden layers corroborated the theoretical predictions: If we initialized weights as indicated by the theory, the standard back-propagation algorithm was both highly successful and efficient at training deep neural networks using sigmoid activation functions., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Vitrimers are a third class of polymers gathering the mechanical properties and solvent resistance of 3D thermosets and the reprocessability of thermoplastics. This unique behaviour is due to the triggering of certain covalent exchange reactions that allow the network to rearrange upon application of a stimulus. The constitutive feature of vitrimers is the adoption of a glass-like viscosity during the rearrangement of the network, often due to an associative mechanism for the exchange reaction. Transesterification networks are one of the most studied type of vitrimers that usually require the incorporation of a catalyst, implying the associated drawbacks. Following up on a recent report on catalyst-free transesterification vitrimers in which the ester functions are particularly reactive thanks to the presence of fluorine atoms in α- or β-position, parallel DFT calculations and an experimental kinetic study on model molecules are presented in order to quantitatively assess the effect of neighbouring fluorinated groups on the transesterification reaction rate., (© 2022 Wiley-VCH GmbH.)

Making decisions is an important aspect of people's lives. Decisions can be highly critical in nature, with mistakes possibly resulting in extremely adverse consequences. Yet, such decisions have often to be made within a very short period of time and with limited information. This can result in decreased accuracy and efficiency. In this paper, we explore the possibility of increasing speed and accuracy of users engaged in the discrimination of realistic targets presented for a very short time, in the presence of unimodal or bimodal cues. More specifically, we present results from an experiment where users were asked to discriminate between targets rapidly appearing in an indoor environment. Unimodal (auditory) or bimodal (audio-visual) cues could shortly precede the target stimulus, warning the users about its location. Our findings show that, when used to facilitate perceptual decision under time pressure, and in condition of limited information in real-world scenarios, spoken cues can be effective in boosting performance (accuracy, reaction times or both), and even more so when presented in bimodal form. However, we also found that cue timing plays a critical role and, if the cue-stimulus interval is too short, cues may offer no advantage. In a post-hoc analysis of our data, we also show that congruency between the response location and both the target location and the cues, can interfere with the speed and accuracy in the task. These effects should be taken in consideration, particularly when investigating performance in realistic tasks., Competing Interests: The authors have declared that no competing interests exist.